Vulcanizable polymerization product and process of producing same



UNITED STATES 'PATENT* OFFICE plastic and capable of being more easily worked The treatment oi the polymerization products m riz tion produ ts provi ed with S h st ill emulsification, drawing out into thinsheets or as stabilizers of amines and of phenols, at least are m u, t work may b transformed mto be substituted by a hydroxyl group. Phenols of ing to my invention not only results in a conmethane),bet -11 91 -fi' tribution of theadditions,.into vulcanizates which product, by spraying their solution upon the finely m monaphthalenq 2-phenyl-amhlonitpli- 55 merizatioh p oduct obtained the'reirom w to- Patented Noy.3,1942 I VULCANIZABLE POLTION PRO!)- 7 UCT-AND PROCESS 01" PRODUCING SAME Ewald Zaueker. Schkopau, Germany: vested in i the Alien Property custodian No Drawinl. Application April 3,1940, Serial No. 327,835. In Germany April 1, 1939 V A 6 Claims. (01.260-36) Y The present invention relates to a process of thalene. 4'-tolyle1-n phthylamine, 2.2'-dinaphproducing plasticized polymerization products cathylamine, 2.7-naph 'lenediamine or 1.4-dipable of being vulcanized and the products, obbeta-naphthylaminobenaene. In the case of polytained thereby. merization products very sensitive to oxygen the vulcanizable polymerization products of hydroamines are preferably added already before the carbons having conjugated double linkages or of polymerization, if they will not hamper the same; their interpolymerization products with other or directly after its completion. The amines may unsaturated compounds, such as styrene or acrylbe added either together with the phenols or sepic nitrile, sometimes possess in insumcient plasarately, in concentrated form or'in solution or ticity by which the further processing voi such v.10 suspension, as the state of the polymerization products is rendered more diflicult. while it is products. may require, i. e. whether this be in known that natural rubber may be rendered more compact or emulsified or dissolved state.

by subjecting it to a gentle oxidation, synthetic, to which the said amines'and phenols'have been rubber-like polymerization products are liable to added, with oxygen or agents supplying oxygen turn hard and brittle or glutinous under the inis preferably carried out at elevated temperafluence of atmospheric oxygen thus losing their ture'and, according to the intensity of action. valuable properties. leads to products of more or. less increased plas- Since oxygen or agents supplying oxygen det ticity. Whereas in the case 0! a thorough mixmental y af ec t ose sy t t Products ing in or an agent supplyin oxygemthe compactat 'room temperature, an addition of so-called ness and shape of the polymerization product are s il is required p ve or -1 fd the of little importance,-a large superficial area has. aforesaid detrimental enacts.- .When the poly,- to be provided itor- (for example by dissolution.

ers are treated for pla tifl at onwit osyse o 2 grinding) when the plastiflcation is carried out a ents supplyin ox e ra her an ten with air or an aqueous medium supplyin osvsen treatment is necessary in order to cause, Such es for example solutions of hydrogen peroxide stabilized ro s to b degraded into more p -v or persalts- It is essential in this treatment that tic products. the contact between the polymerization product Ihave now found that vulcanizabie polymei'izsand the mediu yielding oxygen should be so tion p o m y be el iz un o d intimate that suflicient oxygen-be available also ably milder conditions by treating them with oxinside t polymemuon d t v ygen or agents supplyin xy in the Presence In this manner polymerization products which one nuclear hydmseu m f which i r l it products or good plasticity and which may be by a hydro rb rfldiole which radlcle 8611 1118? worked with greater ease. The process accordthe said kind are, for ex p o-cresol, siderable economy of time and power in the plasthymol. p-i o l p'mtylphenoltiflcation of polymerization products, but also aldecyl-phenol, p-cyolohexvlohe ol. c-benzylrheml lows of trans! rming'the plasticized polymerizaor p-ben lphe i il tion products, by the. good incorporation and dis-. and 2.2'-dihydroxyd1ph m These llhnolfl may are superior in quality-to those hitherto obtained.

be added eith r directly after the Mm The following example servesto illustrate how or whi e h p ly a Products are a my present invention may be carried out in pracworked up or further processe for example by j tice, but the invention is not restricted to the a addins-their alkaline solution or to m example, r are lpywelght,

the aqueous dispersion or the p lymerization; Example ed erization product or by mixins A 3 per, cent solutionot phenyl-p-naphthyl- 532: on l e x i i ixins roller. amine in benzene is added to an aqueous dispermong suitable stabilizing amines 1 may mension of an interpolymerization product from '15 uonflprimary, secondary, or tertiary mon or I parts of butadiene and 25 parts of styrene obpolyamines, tor example dime 'laniline. z-ditamed-by emulsion-polymerization; The polyagulation is incorporated on the mixing roller with 2 per cent 01' one of the phenols set out below. The mixture isreduced by grinding'to a crumbly state and then treated with compressed air at 3.5 atm. and at 130 C. for '10 and 100 minutes, respectively. The degree of plasticity obtained in this way is ascertained by measuring the viscosity of a solution of the treatedproduct in benzene. The plasticity is the greater, the lesser its viscosity measured incentipoise (c. p.)' The following results were obtained:

. Viscosity altera treatment oi- Addition 70 minutes 4-isooctylphenol.. 10.

Hyclohexylphenol. 1i. 9 2-benzylphenol ll. 9 i-benzylphenoi 7. 8 2.2-dihydroxydiphenyl l6.

The same polymerization product added with phenyl-p-naphthylamine alone is insoluble but strongly swellable in benzene. By heating it in compressed air at 3.5 atm..and at 130 C. for 100' minutes'it does not become soluble. By heating it in compressed air at 140 C. after 100 minutes a viscosity of 186 c. p. and after 160 minutesa viscosity of 105.9 c. p. is obtained.

What I claim is:

1. Process of plasticizing synthetic rubber resulting from the emulsion polymerization of an open chain dioleflne which comprises subjecting the synthetic rubber to an oxidizing treatment in the presence of an aromatic stabilizing agent containing an amino group and. selected from the class consisting oi dimethylaniline, 2-dim'ethylaminonaphthalene. 2-phenylaminonaph-' thaiene, 4'-tolyl,-l-naphthylamine, 2.2'-'-dinaphthylamine, 2.7-naphthylene diamine and 1.4-dip-naphthylamino benzene and of a phenol atleast one nuclear hydrogen atom oi which is substituted by a radicle selected from the group consisting of hydrocarbon radicles and hydroxysubstituted hydrocarbon radicles, the phenol beingotherwise unsubstituted. 2. The process of piasticizing synthetic rubber hydrocarbon radicles, the phenol being otherwise unsubstituted.

3. The process of plasticizing synthetic rubber resulting from the emulsion polymerization of butadiene and styrene ing ,the

which comprises subjectsynthetic rubber to an oxidizing treatment in the presence of an aromatic stabilizing agent containing an amino group and selected from the class consisting oi dimethylaniline, 2- dimethylaminonaphthalene, 2 phenylaminonaphthalene, 4'-tolyl-l-naphthylamine, 2.2'-dinaphthlamine, 2.7-naphthylene diamine and 1.4- di-p-naphthylamino benzene and of a phenol at least one nuclear hydrogen atom oi which is substituted by a radicle selected from the group consisting of hydrocarbon radicles and hydroxy-. substituted hydrocarbon radicles, the phenol being otherwise unsubstituted.

4. Synthetic rubber resulting from the emulsion polymerization of an open chain dioleflne, plasticized by 'an oxidizing treatment in the presence of an aromatic stabilizing agent containing an amino group and selected from the class consisting oi dimethylaniline, 2-dimethylaminonaphthalene, 2-phenylaminonaphthalene, 4'-

tolyl- 1 naphthylamine, 2.2'-dinaphthylamine,

2.'7-naphthylene diamine and 1.4-di-p-naphthylamino benzene and otzavphenol at least one nuclear hydrogen atom' otgwhich is substituted by a radicle selected from the group consisting of hydrocarbon radicles and hydroxy-substituted hydrocarbon radicles, the phenol being otherwise unsubstituted.

5. Synthetic rubber resulting from the emulsion polymerization ofa mixture of an open chain dioleflne and another organic compound polymerizable under the same conditions plasticized by an oxidizing treatment in the presence oi an aromatic stabilizing agent containing an amino group selected from the class consisting oi dimethylaniline, 2-dimethylaminonaphthalene, 2- phenylaminonaphthalene, 4 tolyl-l-naphthylamine, 2.2'-dinaphthylamine, 2.7-naphthylene diamine and- 1.4-di-p-naphthylamino benzene and of a phenol at least one nuclear hydrogen atom of whichis substituted by a radicle selected from the group consisting of hydrocarbon radicles and hydroxy-substituted hydrocarbon raditolyl 1 naphthylamine, 2.2'-di naphthylamine,

cles, the phenol being otherwise unsubstituted.

6. Synthetic .rubber resulting from the emulsion' polymerization of butadiene and styrene,

plasticized by an oxidizing treatment in the presence of an aromatic stabilizing agent containing an amino group and selected from the class consisting of dimethylaniiine, Z-dimethylaminonaphthalene, 2-phenylaminonaphthalene, 4'-

2.7-naphthylene diamine and 1.4-di-p-naphthylamino benzene and of a phenol at least one nuclear lwdrogen atom of which is substituted by a radicle selected from the group consisting oi hydrocarbon radicles and hydrozw-substituted hydrocarbon radicles, the phenol being otherwise unsubstituted. Y

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